JP2977569B2 - Method and apparatus for operating a gas turbine by introducing additives - Google Patents
Method and apparatus for operating a gas turbine by introducing additivesInfo
- Publication number
- JP2977569B2 JP2977569B2 JP1501246A JP50124689A JP2977569B2 JP 2977569 B2 JP2977569 B2 JP 2977569B2 JP 1501246 A JP1501246 A JP 1501246A JP 50124689 A JP50124689 A JP 50124689A JP 2977569 B2 JP2977569 B2 JP 2977569B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- magnesium compound
- magnesium
- dissolved
- gas turbine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J7/00—Arrangement of devices for supplying chemicals to fire
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
- F23L7/002—Supplying water
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
- F23L7/002—Supplying water
- F23L7/005—Evaporated water; Steam
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
【発明の詳細な説明】 本発明は、請求の範囲第１項の上位概念部分に記載の
ガスタービンの運転方法および請求の範囲第７項の上位
概念部分に記載の装置に関する。The invention relates to a method for operating a gas turbine according to the preamble of claim 1 and an apparatus according to the preamble of claim 7.
ヨーロッパ特許第Ａ−0193838号公報において、燃焼
領域に水あるいは蒸気を注入することもできるいわゆる
ハイブリッド形バーナが知られている。バーナ構造の詳
細についてはこの公報を明確に引用する。不活性物質を
追加的に注入する別のバーナも、ドイツ連邦共和国特許
第Ａ−3606625号公報で公知である。水および（又は）
蒸気は、例えば燃焼室の燃焼領域に、そこの温度を低下
して環境に対して有害なNOXの発生を低減するために噴
射して入れられる。From EP-A-0193838, a so-called hybrid burner is known, in which water or steam can also be injected into the combustion zone. The details of the burner structure are explicitly cited in this publication. Another burner for additionally injecting inert substances is also known from DE-A-3606625. Water and / or
Steam, for example in the combustion zone of the combustion chamber, is placed by spraying in order to reduce the occurrence of harmful NO X to the environment by reducing the bottom of temperature.
更に従来技術からは、例えばガスタービンの構造部品
を損傷から保護するために、ガスタービンの燃焼領域に
おいて燃料に添加物を混合することが知られている。特
にバナジウム含有燃料例えば特定の重油に関しては問題
がある。バナジウムは高温ガスに曝される構造部品特に
ガスタービンの翼に、強い侵食性を有し保護酸化膜を急
速に解かしてしまう低融点ののバナジウム化合物を形成
する。これは高温腐食を著しく速めるおそれがある。こ
の腐食を避けるために、燃料に金属化合物を添加するこ
とが知られている。この金属化合物は燃焼する際にバナ
ジウムと反応し、バナジン酸塩を形成する。このバナジ
ン酸塩は、ガスタービン翼の一般的な温度において固形
で存在するような高い融点を有する。多くの金属化合物
の中で特にマグネシウムの金属化合物が最適である。何
故ならば、マグネシウムの過剰量が十分であるとき、11
59℃で初めて溶解するマグネシウム・オルトバナジン酸
塩（Mg3V2O8）が生ずるからである。他方ではそのマグ
ネシウム含有被膜はタービン翼から良好に除去できる。
従来においてマグネシウムは燃料に油溶性化合物、コロ
イド懸濁液の形で混合されるか、あるいは乳化しなけれ
ばならない水溶性塩の形で混合される。Furthermore, it is known from the prior art to add additives to the fuel in the combustion area of the gas turbine, for example to protect structural components of the gas turbine from damage. In particular, there are problems with vanadium-containing fuels, such as certain heavy oils. Vanadium forms low melting point vanadium compounds that are highly aggressive and rapidly dissolve protective oxide films on structural components exposed to high temperature gases, especially gas turbine blades. This can significantly accelerate hot corrosion. To avoid this corrosion, it is known to add metallic compounds to the fuel. This metal compound reacts with vanadium when burning to form a vanadate. The vanadate has such a high melting point that it exists as a solid at the typical temperatures of gas turbine blades. Of the many metal compounds, the metal compound of magnesium is particularly optimal. Because when the excess of magnesium is sufficient, 11
This is because magnesium orthovanadate (Mg 3 V 2 O 8 ), which first dissolves at 59 ° C., is produced. On the other hand, the magnesium-containing coating can be successfully removed from the turbine blade.
Conventionally, magnesium is mixed with the fuel in the form of an oil-soluble compound, a colloidal suspension, or a water-soluble salt which must be emulsified.
油溶性付加物の製造は非常に経費がかかり、コストが
高くなり、これは例えばバナジウム含有量が高いとき燃
料の使用を不経済にする。価格的に有利な非油溶性のマ
グネシウム化合物を懸濁液あるいは乳濁液として混合す
ることは安定性について重大な問題を生じ、設備的にか
なりの経費を必要とする。マグネシウム酸化物懸濁液は
バーナノズルを損耗するおそれがある。オーストラリア
特許第Ｂ−496757号公報からは、燃料と乳化された水に
溶けた硫酸マグネシウムを使用することが知られてお
り、本発明はこれから出発している。その燃料との配合
および混合は非常に経費がかかり、一定に保つことは困
難である。従ってほとんどすべての使用状態において、
従来においては高価な油溶性付加物によらざるを得なか
った。The production of oil-soluble adducts is very expensive and costly, which makes the use of fuels uneconomic, for example when the vanadium content is high. The incorporation of a non-oil soluble magnesium compound as a suspension or emulsion, which is cost-effective, poses a serious stability problem and requires considerable equipment expenditure. The magnesium oxide suspension may wear the burner nozzle. From Australian Patent B-496757 it is known to use magnesium sulfate dissolved in fuel and emulsified water, and the present invention is about to start. The blending and mixing with the fuel is very expensive and difficult to keep constant. Therefore, in almost all use conditions,
Conventionally, expensive oil-soluble adducts have to be used.
こののような技術的背景に基づいて本発明の課題は、
上述した問題を解消した状態で燃焼過程にマグネシウム
を確実に且つ経済的に添加できる方法とその装置を提供
することにある。特にバナジウム含有燃料の燃焼過程に
水に溶けた硫酸マグネシウムを添加することを容易に且
つ安価にしようとすることにある。Based on such a technical background, the object of the present invention is to
An object of the present invention is to provide a method and an apparatus capable of reliably and economically adding magnesium to a combustion process while solving the above-mentioned problems. In particular, it is an object of the present invention to easily and inexpensively add magnesium sulfate dissolved in water to a combustion process of a vanadium-containing fuel.
この課題を解決するために、本発明は請求の範囲第１
項の特徴部分に記載の方法および請求の範囲第６項記載
の装置を提案する。有利な実施態様は各従属請求の範囲
に挙げられている。In order to solve this problem, the present invention is directed to Claim 1
A method and a device according to claim 6 are proposed. Advantageous embodiments are specified in the respective dependent claims.
水に溶けたマグネシウム化合物を水と共にバーナに注
入することは、水に溶けたマグネシウム化合物を燃料と
乳化するよりも、工程上極めて容易に制御できる。これ
によって燃料におけるバナジウム成分に対比して注入す
べきマグネシウム成分を正確に配合することが問題なし
に実行できる。バーナにおける必要な添加装置は特に経
費がかからず、排気ガス中のNOXの減少に関係して既に
実証されている。水に溶けたマグネシウム化合物を炎に
直接注入することによって、実際には燃料と共に注入す
る場合と同じ効果が得られる。経済的に有利であり簡単
に水に溶けるマグネシウム化合物として好適には硫酸マ
グネシウムが挙げられる。燃料中のバナジウム成分の重
量％に対して約３倍の重量％のマグネシウムを添加する
と良い。その場合、水溶性のマグネシウム化合物の水中
濃度は、燃料の容積％に対して約10分の１の容積％のマ
グネシウム溶解水が注入されねばならないように、調整
させられる。これは技術的に問題はない。何故ならば、
既に別の目的において水を多くの割合で注入することが
行われているからである。Injecting a magnesium compound dissolved in water together with water into a burner can be controlled much more easily in the process than emulsifying a magnesium compound dissolved in water with a fuel. This makes it possible to mix the magnesium component to be injected accurately with respect to the vanadium component in the fuel without any problem. Added equipment needed in the burner is not applied particularly expenses, have already been demonstrated in relation to the reduction of the NO X in the exhaust gas. Injecting the magnesium compound dissolved in water directly into the flame actually has the same effect as injecting with the fuel. A magnesium compound which is economically advantageous and easily soluble in water is preferably magnesium sulfate. It is preferable to add about 3% by weight of magnesium with respect to the weight percentage of the vanadium component in the fuel. In that case, the concentration of the water-soluble magnesium compound in the water is adjusted so that about one tenth of the volume of magnesium-dissolved water must be injected with respect to the volume of the fuel. This is not technically a problem. because,
This is because water is already injected at a high rate for another purpose.
全過程を説明するために以下にデータについても述べ
る。The data will be described below to explain the whole process.
MgSO4（硫酸マグネシウム）は水に20℃で25.8％が、
０℃で20.9％が溶ける。従ってバーナの火炎中では次の
反応が進行する。MgSO 4 (magnesium sulfate) is 25.8% in water at 20 ° C,
20.9% melts at 0 ° C. Therefore, the following reaction proceeds in the burner flame.
3MgSO4＋V2O5→Mg3V2O8＋3SO3 硫酸によって追加的に導入される硫黄の量は、一般に
燃料に含まれる硫黄の量に比べて問題とならない。また
油溶性マグネシウム化合物の混合に比べて、燃焼過程お
よび射出上の欠点も生じない。The amount of sulfur additionally introduced by 3MgSO 4 + V 2 O 5 → Mg 3 V 2 O 8 + 3SO 3 sulfuric acid is generally not a problem compared to the amount of sulfur contained in the fuel. Further, compared with the mixing of an oil-soluble magnesium compound, there are no drawbacks in the combustion process and injection.
必要な量については以下の実施例を参照して説明す
る。The required amount will be described with reference to the following examples.
燃料中にバナジウムが300ppmの非常に高い濃度で含有
されており、マグネシウムとバナジウムの配合比が3:1
であると仮定した場合、燃料消費量が10kg/secのガスタ
ービンは１時間当たり約160kgのMgSO4を必要とする。濃
度が20％のMgSO4溶液が水に入れられるとき（これは溶
解限度から十分に離れている）、必要な溶液量は１時間
当たり800kgないし670である。The fuel contains very high concentration of 300ppm vanadium, and the mixing ratio of magnesium and vanadium is 3: 1
, A gas turbine with a fuel consumption of 10 kg / sec requires about 160 kg of MgSO 4 per hour. When a 20% strength MgSO 4 solution is placed in water (well off the solubility limit), the required solution volume is 800 kg to 670 per hour.
本発明の方法を実施するための装置は、請求の範囲第
６項、第７項および第８項に記載されている。それに従
ってそれ自体は公知のバーナに本発明に基づく方法を実
施するための添加装置が必要であり、即ち水に溶けてい
るマグネシウム化合物の補助貯蔵タンク、および燃焼室
に水ノズルを介して注入を行う配合装置が必要である。Apparatus for carrying out the method of the invention is described in claims 6, 7 and 8. Accordingly, a burner known per se requires an addition device for carrying out the method according to the invention, i.e. an auxiliary storage tank of magnesium compounds dissolved in water, and injection into the combustion chamber via a water nozzle. A compounding device to perform is required.
本発明の実施例は図面に概略的に示されている。その
場合例えば、ヨーロッパ特許第Ａ−0193838号公報に詳
細に記載されているバーナが使用されている。従ってこ
のバーナ自体の構造の詳細な説明は省略する。重要なこ
とはただ、バーナ１が水の注入装置２および（又は）蒸
気の注入装置３を有していることだけである。予混合バ
ーナ、拡散バーナあるいはいわゆるハイブリッドバーナ
を対象とするか否かは決定的なものではない。本発明に
基づいてかかるバーナには少なくとも１つの貯蔵タンク
４が付設されており、この貯蔵タンク４は配合装置５を
介して水および（又は）蒸気の注入装置２、３に接続さ
れている。Embodiments of the present invention are schematically illustrated in the drawings. In this case, for example, burners described in detail in EP-A-0193838 are used. Therefore, a detailed description of the structure of the burner itself is omitted. All that matters is that the burner 1 has a water injector 2 and / or a steam injector 3. Whether a premix burner, a diffusion burner or a so-called hybrid burner is intended is not critical. According to the invention, such a burner is provided with at least one storage tank 4, which is connected via a compounding device 5 to water and / or steam injection devices 2, 3.
本発明は特に、常にあるいは一時的にバナジウム含有
燃料が燃焼されねばならないガスタービン設備に対して
適用している。The invention has particular application to gas turbine installations in which a vanadium-containing fuel must be burned, always or temporarily.
フロントページの続き (56)参考文献 特開 昭57−89485（ＪＰ，Ａ) 特開 昭53−148611（ＪＰ，Ａ) 特開 昭60−186597（ＪＰ，Ａ) 特開 昭62−227096（ＪＰ，Ａ) 特公 昭59−47141（ＪＰ，Ｂ２)Continuation of front page (56) References JP-A-57-89485 (JP, A) JP-A-53-148611 (JP, A) JP-A-60-186597 (JP, A) JP-A-62-227096 (JP) , A) Japanese Patent Publication No. Sho 59-47141 (JP, B2)
Claims (8)
ビンの運転方法であって、ガスタービンが少なくとも１
つのバーナを燃焼室に有しており、燃焼室に添加物とし
て水に溶けたマグネシウム化合物が導入される方法にお
いて、水に溶けたマグネシウム化合物が、水と一緒に別
に燃焼室に注入され、V2O5成分当たり１成分より多くの
MgO成分を有するバナジン酸塩が形成されることを特徴
とするガスタービンの運転方法。1. A method of operating a gas turbine in which a vanadium-containing fuel is burned, wherein the gas turbine includes at least one gas.
In a method in which two burners are provided in the combustion chamber, and a magnesium compound dissolved in water is introduced as an additive into the combustion chamber, the magnesium compound dissolved in water is separately injected into the combustion chamber together with the water, and V More than 1 component per 5 components of 2 O
A method for operating a gas turbine, wherein a vanadate having an MgO component is formed.
にバーナの火炎に直接吹きつけられることを特徴とする
請求の範囲第１項記載の方法。2. The method according to claim 1, wherein the water is blown directly to the burner flame together with the dissolved magnesium compound.
に硫酸マグネシウム（MgSO4）であることを特徴とする
請求の範囲第１項又は第２項記載の方法。3. The method according to claim 1, wherein the magnesium compound is a magnesium salt, particularly magnesium sulfate (MgSO 4 ).
倍の重量％のマグネシウムが注入されることを特徴とす
る請求の範囲第１項ないし第３項のいずれか１つに記載
の方法。4. The combustion chamber contains 3% by weight of vanadium.
4. The method according to claim 1, wherein twice the weight percent of magnesium is injected.
燃料の容積％に対して約10分の１以下の容積％のマグネ
シウム化合物溶解水が注入されるように、調整されてい
ることを特徴とする請求の範囲第１項ないし第４項のい
ずれか１つに記載の方法。5. The concentration of a water-soluble magnesium compound in water is as follows:
5. The method according to claim 1, wherein the amount of the magnesium compound-dissolved water is about 1/10 or less of the volume of the fuel. The method according to one.
ための装置を備えたバーナ（１）を有し、マグネシウム
化合物溶解水に対する少なくとも１つの補助貯蔵タンク
が、配合装置（５）を介してバーナ（１）における水あ
るいは蒸気の注入装置（２、３）に接続されていること
を特徴とする請求の範囲第１項ないし第５項のいずれか
１つに記載の方法を実施するためにの装置。6. A burner (1) provided with a device for injecting water and / or steam into a combustion chamber, wherein at least one auxiliary storage tank for magnesium compound-dissolved water comprises a compounding device (5). 6. The method according to claim 1, which is connected via a water or steam injection device (2, 3) in the burner (1). Equipment for
ていることを特徴とする請求の範囲第６項記載の装置。7. The device according to claim 6, wherein the storage tank has a capacity of at least 1 m 3 .
単位時間当たりに導入される燃料容積の約10分の１の容
積のマグネシウム化合物溶解水が注入されるように、寸
法づけられていることを特徴とする請求の範囲第６項又
は第７項記載の装置。8. An apparatus for injecting water or steam (2, 3)
8. The apparatus according to claim 6, wherein the magnesium compound-dissolved water is injected at a volume of about one tenth of a fuel volume introduced per unit time. Equipment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3808016.8 | 1988-03-10 | ||
| DE3808016 | 1988-03-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03503303A JPH03503303A (en) | 1991-07-25 |
| JP2977569B2 true JP2977569B2 (en) | 1999-11-15 |
Family
ID=6349401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1501246A Expired - Fee Related JP2977569B2 (en) | 1988-03-10 | 1989-01-19 | Method and apparatus for operating a gas turbine by introducing additives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0533652B1 (en) |
| JP (1) | JP2977569B2 (en) |
| DE (1) | DE58909147D1 (en) |
| IN (1) | IN171209B (en) |
| WO (1) | WO1989008803A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580683B1 (en) * | 1991-04-25 | 1995-11-08 | Siemens Aktiengesellschaft | Burner arrangement, especially for gas turbines, for the low-pollutant combustion of coal gas and other fuels |
| EP0717813B1 (en) * | 1993-09-08 | 2000-03-08 | Siemens Aktiengesellschaft | Method of operating a gas turbine using an additive feed |
| EP0735002A1 (en) * | 1995-03-31 | 1996-10-02 | Siemens Aktiengesellschaft | Method and apparatus for dissolving a magnesium compound in water |
| JP2002372233A (en) * | 2001-06-14 | 2002-12-26 | Seiji Inoue | Auxiliary equipment of boiler |
| EP1329614A1 (en) * | 2002-01-21 | 2003-07-23 | Siemens Aktiengesellschaft | Burner and Process for Operating a Burner, in particular for a gas turbine engine |
| EP2318494B1 (en) | 2008-07-08 | 2013-11-27 | The Lubrizol Corporation | Marine diesel cylinder lubricant |
| DE102009014026A1 (en) * | 2008-12-03 | 2010-06-10 | Ernest Stangl | Method for generating thermal energy as e.g. electrical energy, in distributed power plant, involves burning fuel in container in heat- or power plant using oxygen source, and supplying carbon dioxide and oxygen mixture for burning fuel |
| US8123821B2 (en) * | 2009-02-10 | 2012-02-28 | General Electric Company | Regulating vanadium inhibitor in a gas turbine |
| EP2230458A1 (en) | 2009-03-17 | 2010-09-22 | Siemens Aktiengesellschaft | Burner assembly for fluid fuels and method for producing a burner assembly |
| EP2264370B1 (en) | 2009-06-16 | 2012-10-10 | Siemens Aktiengesellschaft | Burner assembly for a firing assembly for firing fluid fuels and method for operating such a burner assembly |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB731242A (en) * | 1950-06-28 | 1955-06-08 | Power Jets Res & Dev Ltd | Improvements in or relating to fuel oils and the combustion of fuel oils |
| ES454017A1 (en) * | 1976-12-07 | 1977-11-16 | Alentorn Ricos S L R | Improvements in facilities for the treatment of combustión through metal oxides. (Machine-translation by Google Translate, not legally binding) |
| AU496757B2 (en) * | 1977-02-03 | 1977-04-21 | The Percom Company, Inc | Compositions and methods for inhibiting corrosion and ash deposition in fossil fuel burning equipment |
| DE2932676C2 (en) * | 1979-08-11 | 1983-01-27 | L. & C. Steinmüller GmbH, 5270 Gummersbach | Process for binding sulfur, chlorine and fluorine compounds during combustion |
| US4375359A (en) * | 1979-11-02 | 1983-03-01 | Dearborn Chemical Company Limited | Water based fireside additive |
| GB2095283B (en) * | 1981-02-09 | 1984-08-01 | Polarchem Ltd | Method for the prevention of deposits on or the removal ofdeposits from heating and ancillary surfaces |
| DE3318374A1 (en) * | 1983-05-20 | 1984-11-22 | Günter 3000 Hannover Hackerodt | Process for the removal of sulphur oxides from combustion gases and apparatus for carrying out the process |
| DE3444469C1 (en) * | 1984-12-06 | 1986-06-19 | L. & C. Steinmüller GmbH, 5270 Gummersbach | Process and round burner for injecting aqueous additive suspensions in the center of a round burner |
-
1989
- 1989-01-19 DE DE58909147T patent/DE58909147D1/en not_active Expired - Fee Related
- 1989-01-19 WO PCT/DE1989/000026 patent/WO1989008803A1/en not_active Ceased
- 1989-01-19 JP JP1501246A patent/JP2977569B2/en not_active Expired - Fee Related
- 1989-01-19 EP EP89901457A patent/EP0533652B1/en not_active Expired - Lifetime
- 1989-03-29 IN IN241/CAL/89A patent/IN171209B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03503303A (en) | 1991-07-25 |
| EP0533652A1 (en) | 1993-03-31 |
| WO1989008803A1 (en) | 1989-09-21 |
| IN171209B (en) | 1992-08-15 |
| EP0533652B1 (en) | 1995-03-29 |
| DE58909147D1 (en) | 1995-05-04 |
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